CN104629496A - Treatment method of modified graphene - Google Patents
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Abstract
The invention discloses a treatment method of modified graphene. The treatment method comprises the following steps: pretreating and oxidizing graphite to obtain purified graphene of which the surface contains hydroxyl groups, also obtaining a long-chain molecule product by virtue of a chemical method, and then promoting reaction by virtue of designing conditions of the chemical method to ensure that long-chain molecules are grafted onto graphene. By virtue of the mode, the dispersion performance of graphene can be improved, and agglomeration can be avoided; the modified long-chain molecules are wide in source, are environment-friendly, and are also beneficial to the improvement of biocompatibility of graphene; and moreover, the provided modified long-chain molecules have relatively more active sites, and more graphene modification can be provided to ensure that obtained modified graphene has the effect of regulating the viscosity of a matrix and can be used for improving the processing and application properties. The method disclosed by the invention is simple and good in use effect.
Description
Technical field
The present invention relates to material science, especially a kind for the treatment of process of modified graphene.
Background technology
Graphene (Graphene) is a kind of novel material of the individual layer sheet structure be made up of carbon atom, is the two-dimensional material only having a carbon atom thickness.
Graphene is thin, the hardest nano material in known world, and single-layer graphene is almost completely transparent, only absorbs the light of 2.3%; Thermal conductivity is up to 5300 W/mK, and higher than carbon nanotube and diamond, under normal temperature, its electronic mobility is more than 15000 cm2/Vs, than CNT (carbon nano-tube) or silicon wafer height, and resistivity only about 10-8 Ω m, than copper or silver lower, be the material that world resistivity is minimum.Because its resistivity is extremely low, the speed of electronic migration is exceedingly fast, and is therefore expected to can be used to develop thinner, conduction speed electronic component of new generation or transistor faster.Because Graphene is in fact a kind of transparent, good conductor, be also applicable to for manufacturing transparent touch screen, tabula rasa or even solar cell.
But with Graphene be the nano material of representative in use because the reasons such as reunions cause it to process and use properties significantly declines, thus seriously limit the application of Graphene.How effectively to improve processing and the use properties of matrix material, the focus that Ze Shi academia and industry member are paid close attention to.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind for the treatment of process of modified graphene, it effectively can improve the dispersiveness of Graphene, improves processing and the use properties of graphene composite material, and with low cost, environmentally friendly, customer service the deficiencies in the prior art.
The present invention is achieved in that the treatment process of modified graphene, comprises the steps,
1) graphite oxide is dissolved in the water completely, obtains the graphite oxide aqueous solution; Then add ammoniacal liquor to stir, after having stirred, treat that solution naturally cools to room temperature, then throw out is leached, and after cleaning-drying, obtain the purifying graphene Graphene-OH of surface containing hydroxyl;
2) calculate by weight, add in organic solvent by 22-27 part gamma carotene and 9-11 part along divinyl acid anhydrides, solid-liquid ratio is 31:60-38:60g/ml; Fully mix, 130-170 DEG C, there is D-A under nitrogen protection and react 3-5h; In reacted mixture, add 90-95 part epoxy chloropropane and 0.6-0.8 part amine bromide again, reflux 5-7h, after being then cooled to 65-75 DEG C, adds excessive sodium hydrate, through washing to obtain long-chain compound; Reaction formula is as follows:
3) purifying graphene Graphene-OH and the step 2 of hydroxyl being contained in the surface obtained in step 1) the middle long-chain compound obtained reacts according to the molar ratio of 1:1, reaction conditions is: the sodium hydroxide of 1/6 molar ratio, temperature are 130-170 DEG C, react 3-5h under nitrogen protection, add the Tetrabutyl amonium bromide backflow 5-10 hour of 0.1-1 part simultaneously, after being cooled to 65-75 DEG C, add excessive sodium hydrate, namely obtain Graphene grafted epoxy gamma carotene through washing, thus achieve the modification to Graphene; Reaction formula is as follows:
The graphite oxide aqueous solution described in the step 1) rotating speed mixed with ammoniacal liquor when stirring is 1000r/min, and the time is 2h:
Compared with prior art, the present invention carries out pre-treatment to graphite oxide, obtains the purifying graphene of surface containing hydroxyl, and obtains long chain molecule product by chemical process, inspire reaction by chemical process design conditions again, long chain molecule is grafted on Graphene.Such mode can improve Graphene dispersiveness, avoid reunite, thus improve its composite processing and use properties, modification long chain molecule wide material sources, environmentally friendly, also help the biocompatibility improving Graphene, and the modification long chain molecule provided has more active site, more Graphene modifications can be provided, make the modified graphene of acquisition have the effect of adjustable matrix viscosity, processing and use properties can be improved.The inventive method is simple, and result of use is good.
Embodiment
Embodiments of the invention 1: the treatment process of modified graphene, comprises the steps,
1) graphite oxide is dissolved in completely in 100ml water, obtains the graphite oxide aqueous solution; Then add mass percent concentration be 20% 100ml ammoniacal liquor stir, the rotating speed 300r/min stirred, time is 2h, after stirring completes, treat that solution naturally cools to room temperature, again throw out is leached, and after cleaning-drying, obtain the purifying graphene Graphene-OH of surface containing hydroxyl;
2) 25g gamma carotene and 9.8g are added in the benzene of 60ml along divinyl acid anhydrides, fully mix, 140 DEG C, there is D-A under nitrogen protection and react 4h; In reacted mixture, add 93g epoxy chloropropane and 0.7g amine bromide again, reflux 6h, after being then cooled to 73 DEG C, add excessive sodium hydrate, through washing to obtain long-chain compound;
3) long-chain compound adding 0.3mol, in the 30ml aqueous solution, adds 0.1mol sodium hydroxide under 120 DEG C of conditions, reacts 3h under condition of nitrogen gas, then adds the Tetrabutyl amonium bromide (Bu of Graphene-OH and 0.2g of 0.3mol
4nBr) reflux 5h, is chilled to 60 DEG C afterwards, then adds excessive sodium hydroxide, be chilled to room temperature after washing, namely obtain Graphene grafted epoxy gamma carotene, thus achieve the modification to Graphene.
Embodiments of the invention 2: the treatment process of modified graphene, comprises the steps,
1) graphite oxide is dissolved in completely in 15ml water, obtains the graphite oxide aqueous solution; Then add mass percent concentration be 25% 120ml ammoniacal liquor stir, the rotating speed stirred is 400r/min, time is 3h, after stirring completes, treat that solution naturally cools to room temperature, again throw out is leached, and after cleaning-drying, obtain the purifying graphene Graphene-OH of surface containing hydroxyl;
2) 22g gamma carotene and 9g are added in the toluene of 60ml along divinyl acid anhydrides, fully mix, 170 DEG C, there is D-A under nitrogen protection and react 4h; In reacted mixture, add 90g epoxy chloropropane and 0.6g amine bromide again, reflux 5h, after being then cooled to 75 DEG C, add excessive sodium hydrate, through washing to obtain long-chain compound;
3) long-chain compound of 0.5mol is added in the 30ml aqueous solution, 0.15mol sodium hydroxide is added under 130 DEG C of conditions, 4h is reacted under condition of nitrogen gas, then the Tetrabutyl amonium bromide backflow 6h of Graphene-OH and 0.5g of 0.5mol is added, be chilled to 70 DEG C afterwards, then add excessive sodium hydroxide, after washing, be chilled to room temperature, namely obtain Graphene grafted epoxy gamma carotene, thus achieve the dispersed modification to Graphene.
Embodiments of the invention 3: the treatment process improving graphene dispersion, comprises the steps,
1) graphite oxide is dissolved in completely in 30ml water, obtains the graphite oxide aqueous solution; Then add mass percent concentration be 25% 150ml ammoniacal liquor stir, the rotating speed 500r/min stirred, time is 4h, after stirring completes, treat that solution naturally cools to room temperature, again throw out is leached, and after cleaning-drying, obtain the purifying graphene Graphene-OH of surface containing hydroxyl; ;
2) 27g gamma carotene and 11g are added in the acetonitrile of 60ml along divinyl acid anhydrides, fully mix, 130 DEG C, there is D-A under nitrogen protection and react 5h; In reacted mixture, add 90g epoxy chloropropane and 0.6g amine bromide again, reflux 4h, after being then cooled to 75 DEG C, add excessive sodium hydrate, through washing to obtain long-chain compound;
3) long-chain compound of 0.8mol is added in the 60ml aqueous solution, 0.3mol sodium hydroxide is added under 140 DEG C of conditions, 5h is reacted under condition of nitrogen gas, then the Tetrabutyl amonium bromide backflow 5h of Graphene-OH and 1g of 0.8mol is added, be chilled to 80 DEG C afterwards, then add excessive sodium hydroxide, after washing, be chilled to room temperature, namely obtain Graphene grafted epoxy gamma carotene, thus achieve the modification to Graphene.
The product that above embodiment obtains is tested, specific as follows:
(trade mark T30S, melt flow rate (MFR) 2.3g/10min, density is 0.92g/cm to modified graphene respectively with 99.97 parts of polypropylene of precise mass fraction 0.03 part of embodiment 1 ~ 3 synthesis
3), carry out extruding pelletization by twin screw extruder after disperseing 30 minutes with ultrasonic disperser.Scanning electronic microscope observation is carried out to blending extrusion material, finds that Graphene is without obvious agglomeration, favorable dispersity.For checking dispersion effect, carry out mechanical property test further.
Gained pellet opens wide placement after 24 hours at 80 DEG C dry 2 hours, then by injection mechanism for polypropylene test bars.After this batten at room temperature places 24 hours, carry out Mechanics Performance Testing, impact property is tested according to ASTM D ~ 256, and tensile property is tested according to ASTM D638 ~ 82a, and bending property is tested according to ASTM D790, and correlated results is in table 1.According to same work program, pure PPT30S is injected as test bars, carry out above-mentioned Mechanics Performance Testing as reference.
Can find from mechanical performance data, modified graphene can significantly improve the mechanical property of matrix material.
Claims (2)
1. a treatment process for modified graphene, is characterized in that: comprise the steps,
1) graphite oxide is dissolved in the water completely, obtains the graphite oxide aqueous solution; Then add ammoniacal liquor to stir, after having stirred, treat that solution naturally cools to room temperature, then throw out is leached, and after cleaning-drying, obtain the purifying graphene Graphene-OH of surface containing hydroxyl;
2) calculate by weight, add in organic solvent by 22-27 part gamma carotene and 9-11 part along divinyl acid anhydrides, solid-liquid ratio is 31:60-38:60g/ml; Fully mix, 130-170 DEG C, there is D-A under nitrogen protection and react 3-5h; In reacted mixture, add 90-95 part epoxy chloropropane and 0.6-0.8 part amine bromide again, reflux 5-7h, after being then cooled to 65-75 DEG C, adds excessive sodium hydrate, through washing to obtain long-chain compound;
3) purifying graphene Graphene-OH and the step 2 of hydroxyl being contained in the surface obtained in step 1) the middle long-chain compound obtained reacts according to the molar ratio of 1:1; reaction conditions is: the sodium hydroxide of 1/6 molar ratio, temperature are 130-170 DEG C, react 3-5h under nitrogen protection; add the Tetrabutyl amonium bromide backflow 5-10 hour of 0.1-1 part simultaneously; after being cooled to 65-75 DEG C; add excessive sodium hydrate; namely obtain Graphene grafted epoxy gamma carotene through washing, thus achieve the modification to Graphene.
2. the treatment process of modified graphene according to claim 1, is characterized in that: the rotating speed mixed with ammoniacal liquor when stirring of the graphite oxide aqueous solution described in step 1) is 400-1000r/min, and the time is 2-4h.
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| CN109851596A (en) * | 2018-09-06 | 2019-06-07 | 华侨大学 | A kind of substitution graphite alkane material and preparation method thereof with stereochemical structure |
| CN110183812A (en) * | 2019-06-13 | 2019-08-30 | 安徽省高等级公路工程监理有限公司 | A kind of preparation method of high durable express highway pavement modified nano composite material |
| CN111705502A (en) * | 2020-06-13 | 2020-09-25 | 佛山市南庄恒安织造厂有限公司 | Manufacturing method of graphene antibacterial fabric |
| CN113929343A (en) * | 2021-10-26 | 2022-01-14 | 浙江和业科技有限公司 | Method for preparing polycarboxylate superplasticizer by using vinyl polyoxyethylene ether |
| CN113980281A (en) * | 2021-11-23 | 2022-01-28 | 广东盈骅新材料科技有限公司 | Epoxy modified silicon resin and preparation method thereof |
| CN114773829A (en) * | 2022-05-20 | 2022-07-22 | 惠特鞋业有限公司 | Wear-resistant sole and preparation method thereof |
| CN115368757A (en) * | 2022-09-01 | 2022-11-22 | 安徽嘉阳新材料科技有限公司 | Preparation process of high-strength high-barrier high-thermal-stability modified graphene powder |
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| CN111705502A (en) * | 2020-06-13 | 2020-09-25 | 佛山市南庄恒安织造厂有限公司 | Manufacturing method of graphene antibacterial fabric |
| CN113929343A (en) * | 2021-10-26 | 2022-01-14 | 浙江和业科技有限公司 | Method for preparing polycarboxylate superplasticizer by using vinyl polyoxyethylene ether |
| CN113980281A (en) * | 2021-11-23 | 2022-01-28 | 广东盈骅新材料科技有限公司 | Epoxy modified silicon resin and preparation method thereof |
| CN113980281B (en) * | 2021-11-23 | 2022-11-15 | 广东盈骅新材料科技有限公司 | Epoxy modified silicon resin and preparation method thereof |
| CN114773829A (en) * | 2022-05-20 | 2022-07-22 | 惠特鞋业有限公司 | Wear-resistant sole and preparation method thereof |
| CN114773829B (en) * | 2022-05-20 | 2023-12-08 | 温州天马新材料科技有限公司 | Wear-resistant sole and preparation method thereof |
| CN115368757A (en) * | 2022-09-01 | 2022-11-22 | 安徽嘉阳新材料科技有限公司 | Preparation process of high-strength high-barrier high-thermal-stability modified graphene powder |
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